Process of dyeing.



I UNITED STATES Patented January 3, 1905.

PATENT OEEIoE.

PROCESS OF DYEING.

SPECIFICATION forming part of Letters Pat nt N 779,228, dated January 3, 1905.

' Application filed October 14, 1903.

To all whom it may concern.-

Be it known that I, HEINRICH MANN, a citizen of Germany, residing at Munich, Germany, have invented certain new and useful Improvements in Processes of Dyeing; and I do hereby declare the following to be 'a full, clear, and exact description of the invention, such as will enable others skilled in theart to which it appertains to make and use the same.

My invention relates to the art of dyeing; and its object is to produce upon animal or vegetable fibers various color effects, such as brown, gray, or blendings of the same. It is to be distinguished in this particular from the processes which result in the production of anilin-black colors.

In carrying out this invention I employ as bases the amin derivatives of benzene or the amin derivatives of naphthalene, as also hydroxyl derivatives of benzene and naphthalene and tertiary amins, all of which for the purposes of this invention are to be considered as the equivalents of the first mentionedviz., the amin derivatives of benzene.

In carrying out the process I form a solution of the amin derivatives of benzene or of one or more -of the equivalents above mentioned and add to such solution a suitable metal salt and hydrogen peroxid. If any free mineral acid would result from employing the metals above indicated, such free mineral acid is neutralized and bound by the addition of a suitable salt of a fatty acid, such as an acetate, an oxalate, or a vinate. The dye-bath so formed must be of such a character that it it will not color a test solution of potassium chromate blue when added thereto. Into the bath so prepared the material to be dyed is immersed, and the solution is warmed,where upon in a short time the material will be dyed. The color produced varies with the materials employed, as will be explained hereinafter.

Substantially all the metal salts, with the exception of the salt of the alkali and alkaliearth metals, may be used in my process. More specifically stated, the metal salt is any metal salt which itself has a pronounced colorthat is to say, is not whiteas, for ex- Serial No. 176,991. (Specimens-l ample, salts of iron, of copper, of chromium, of nickel, of cobalt, of manganese, of platinum, of vanadium, or of cerium. It is immaterial whether these salts contain the higher or lower equivalents of oxygen. The oxidizing agent employed is hydrogen peroxid.

To describe the process involving my invention more in detail, I desire to state that under the said invention equal parts, by weight, of the amin derivatives of benzene and the colored metal salts are caused to coact with hydrogen peroxid in the proportion of one molecule of peroxid to two molecules of the amin derivative in the absence of mineral acids and alkalies. The simultaneous interaction of these three substances under these conditions constitutes the essential part of this invention. This interaction is brought about in the following way: The amin derivative of benzene is dissolved in water Ororganic acid diluted with water. Thereupon hydrogen peroxid is added and the metal salt. Into the bath so prepared the fibers or textile material is immersed. If instead of the organic bases above set forth the salt of such base formed by combining with a mineral acid such, for example, as anilin chloridis employed, the proportion, by weight, of this amin derivative is correspondingly increased, and the mineral acid which is liberated by the addition of the metal salt and hydrogen peroxid is neutralized and bound by the addition of the salt or compound of a fatty acid-such, for example, as sodium acetate. Such salt of an organic acid is to be added in slight excess. The fact that no further free acid exists in the bath may be readily ascertained by testing with sodium chromate. If a solution of this body is not colored blue by a sample from the bath, the said bath contains no further mineral acid.

The proportion of material or the fiber to be dyed and of the reagents above may be varied within large limits, and the shade of the color formed on the fiber varies according to such proportions. WVhen the fiber is immersed in the bath above described, the same is heated and the fiber is mechanically agitated. The dye is formed in this manner and cornbines with the fiber in a nascent state. process will be finished some time after the temperature has risen above centigrade. The dyed fiber is then freed from an excess of dye adhering thereto by washing in water and is then dried. To produce a green with anilin and copper salts together with hydrogen peroxid, the ordinary temperature is sufficient, and the fiber or textile should be {)urged and agitated for several minutes in the A few examples stating the process more in detail will now be given.

I take one kilogram of anilin and dissolve the same in fifteen hundred liters of water, and to this solution I add one kilogram of ferric chlorid, and then I add thereto three hundred and sixty-five grams of hydrogen peroxid, equivalent to the proportion of one molecule of the latter to one molecule of anilin. In this dye-bath I immerse the material to be dyed, the bath being warmed to a temperature of substantially 80 centigrade. After the bath has reached this temperature or risen slightly above the same the goods will be dyed, particularly if they have been well agitated in the bath. Instead of using water as the solvent in this bath a solution of a suitable organic acid-such, for example, as acetic acid-may be employed. Generally speaking, a dilute solution of some organic acid will accomplish the best results. Instead of the anilin proper I may employ a salt of anilin'with a mineral acid-such, for example, as anilin chlorid. In this case 1. 387 kilograms of the anilin salt must be employed, the quantity of the other ingredients of the bath remaining the same as above. When such mineral-acid salt of anilin is employed, sufficient salt of an organic or fatty acid, such as sodium acetate-in the present case one and onehalf kilograms of such acetatemust be added to the bath, in order to bind the free acid involved.

Good results, but other shades of color, will follow if in the above process two kilograms of anilin are employed, the proportion of the other ingredients remaining the same. Other color effects are produced when substituting for the ferric chlorid in the above example sulfate of iron or of copper or nitrate of cobalt or of nickel or of cerium. Other examples of amin derivatives of benzene or equivalents which can be used instead of the anilin above are phenyl-hydrazin, dimethyl-anilin, paraphenylene diamin, benzidin, chromo-sulfate, phenol, resorcin, paramido-phenol, betanaphthol, trinitrophenol, chrysoidin, and Bismarck brown.

The colors produced by my process are very durable under the action of light, water, soap, and chlorid of lime.

The

The advantages of my process are the exactness of the results with regard to color, the variety obtainable by variations in the amount of materials employed, the simplicity of the operation, and its cheapness; Furthermore, one of the chief advantages is the possibility of obtaining with a single organic body an entire series of new colors different from each other by the proper selection of the metal salts. A still further advantage is that no free alkalies or free mineral acids exist in the solution when the material to be dyed is subjected to the same, and hence there can be no injury to the material from such cause.

Having thus fully described my invention, what I claim as new, and desire to secure by Letters Patent of the United States, is

1. The process of dyeing, which consists in submitting the material to be dyed to the action of an amin derivative of benzene in the presence of hydrogen peroxid and a colored metal salt.

2. The process of dyeing, which consists in preparing a bath of an amin derivative of benzene added to hydrogen peroxid and a colored metal salt and immersing the material to be dyed into such bath.

8. The process of dyeing, which consists in preparinga bath of an amin derivative of benzene added to a colored metal salt and hydrogen peroxid in the proportion of one molecule of the hydrogen peroxid to two molecules of the amin derivative and immersing the material to be dyed in such bath.

4. The process of dyeing, which consists in submitting the material to be dyed to the action of an amin derivative of benzene in the presence of hydrogen peroxid and a colored metal salt and in the absence of mineral acid or alkali.

5. The process of dyeing, which consists in preparing a bath of an amin derivative of benzene added to hydrogen peroxid and a colored metal salt and in the absence of mineral acid or alkali.

6. The process of dyeing, which consists in preparing a bath of an amin derivative of benzene added to a colored metal salt and hydrogen peroxid in the proportion of one molecule of the hydrogen peroxid to two molecules of the amin derivative and in the absence of mineral acid or alkali.

7. The process of dyeing, which consists in submitting the material to be dyed to an amin derivative of benzene capable of liberating free mineral acid in the presence of a colored metal salt and hydrogen peroxid and sufficient salt of an organic acid to bind the free mineral acid evolved.

8. The process of dyeing, which consists in preparing a bath of an amin derivative of benzene capable of evolving free mineral acid and adding thereto hydrogen peroxid and a colored metal salt and suflicient salt of an or- IOO ITS

ganic acid to bind the free mineral acid salt of an organic acid to bind the free min- I0 evolved, and immersing the material to be eral acid evolved, and immersing the material dyed into such bath. 7 to be dyed into such bath.

9. The process of dyeing, Which consists in In testimony whereof I affix my signature in 5 preparing a bath of an arnin derivative of benpresence of two Witnesses.

zene and adding thereto a colored metal salt HEINRlCH MANN. and hydrogen peroXid in the proportion of Witnesses: one molecule of the hydrogen-peroxid to two FRED. A. PAULIG,

molecules of the amin derivative and sufficient ABRAHAM SCHLESINGER. 

